CN111394040B - High-performance bi-component polyurethane adhesive and preparation method thereof - Google Patents
High-performance bi-component polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN111394040B CN111394040B CN202010476443.3A CN202010476443A CN111394040B CN 111394040 B CN111394040 B CN 111394040B CN 202010476443 A CN202010476443 A CN 202010476443A CN 111394040 B CN111394040 B CN 111394040B
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- diisocyanate
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 53
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 53
- 239000000853 adhesive Substances 0.000 title claims abstract description 46
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 36
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 claims abstract description 20
- HDTRYLNUVZCQOY-WSWWMNSNSA-N Trehalose Natural products O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-WSWWMNSNSA-N 0.000 claims abstract description 20
- HDTRYLNUVZCQOY-LIZSDCNHSA-N alpha,alpha-trehalose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-LIZSDCNHSA-N 0.000 claims abstract description 20
- 229920005862 polyol Polymers 0.000 claims abstract description 16
- 150000003077 polyols Chemical class 0.000 claims abstract description 16
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 14
- 229920000570 polyether Polymers 0.000 claims abstract description 14
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 13
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 12
- 125000000129 anionic group Chemical group 0.000 claims abstract description 12
- 239000012975 dibutyltin dilaurate Substances 0.000 claims abstract description 12
- 150000002009 diols Chemical class 0.000 claims abstract description 12
- WPEOOEIAIFABQP-UHFFFAOYSA-N hexanedioic acid;hexane-1,6-diol Chemical compound OCCCCCCO.OC(=O)CCCCC(O)=O WPEOOEIAIFABQP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 12
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 229920003009 polyurethane dispersion Polymers 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000005303 weighing Methods 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 230000001804 emulsifying effect Effects 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002518 antifoaming agent Substances 0.000 claims description 6
- 238000009775 high-speed stirring Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000002562 thickening agent Substances 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003431 cross linking reagent Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 5
- DDKIXUQHRSUCMN-UHFFFAOYSA-N n-butylbutan-1-amine;propan-2-one Chemical compound CC(C)=O.CCCCNCCCC DDKIXUQHRSUCMN-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- -1 adipic acid 1,6 hexanediol ester Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920005586 poly(adipic acid) Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3218—Polyhydroxy compounds containing cyclic groups having at least one oxygen atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5072—Polyethers having heteroatoms other than oxygen containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention belongs to the technical field of polyurethane adhesives, and particularly relates to a high-performance bi-component polyurethane adhesive and a preparation method thereof. The component A of the double-component polyurethane adhesive comprises the following components: isophorone-diisocyanate, sulfonated polyether polyol, polycaprolactone diol, dibutyltin dilaurate, dimethylol butyric acid, acetone, aqueous anionic polyurethane dispersion, triethylamine and ethylenediamine, wherein the component B comprises the following components: isophorone-diisocyanate, 1,6 hexanediol adipate and trehalose. The double-component polyurethane adhesive has the characteristics of high solid content, low viscosity, high bonding strength, good heat resistance and water resistance and no pollution. The preparation method has the advantages of simple process, convenient operation, easy recovery and treatment of the solvent and cost saving.
Description
Technical Field
The invention belongs to the field of polyurethane adhesives, and particularly relates to a high-performance bi-component polyurethane adhesive and a preparation method thereof.
Background
The double-component polyurethane adhesive is mainly composed of a hydroxyl-containing water-based polyol component (component A) and an isocyanate-containing polyisocyanate component (component B). In addition, the system also contains other auxiliary agents with special purposes. The component A and the component B are separately packaged, the two components are uniformly mixed before use, and the urethane is formed by the crosslinking reaction of hydroxyl groups (-OH) in polyol and isocyanate groups (-NCO) in polyisocyanate by adjusting the proportion of the component A and the component B, so that the aspects of the strength, the curing time and the like of the polyurethane material can be changed.
At present, the viscosity of the prepared mixed components of the two-component polyurethane adhesive sold on the market is high, so that the fluidity is poor, the leveling property of the two-component polyurethane adhesive is further influenced, the gluing amount is increased, if the viscosity is reduced, the bonding strength of the two-component polyurethane adhesive is low, and the peeling strength of the two-component polyurethane adhesive for bonding low-polarity shoe materials such as SBS and the like cannot meet the requirement, so that the search for the two-component polyurethane adhesive which has high solid content, low viscosity and high bonding strength is the subject of research of technical personnel in the field.
Disclosure of Invention
The invention provides a high-performance bi-component polyurethane adhesive and a preparation method thereof on the basis of overcoming the prior art. The prepared two-component polyurethane adhesive has the characteristics of high solid content, low viscosity, high bonding strength, good heat resistance and water resistance and no pollution; the preparation method of the polyurethane adhesive has the advantages of simple process, convenient operation, easy solvent recovery and treatment and cost saving.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, a high performance two-component polyurethane adhesive is provided, comprising component a and component B:
the component A comprises the following components in parts by weight: 15-30 parts of isophorone-diisocyanate, 5-10 parts of polycaprolactone diol, 0.5-3 parts of dibutyltin dilaurate, 1-3 parts of dimethylolbutyric acid, 4-8 parts of acetone, 4-2 parts of water-based anionic polyurethane dispersion U540.5, 1-6 parts of triethylamine and 4-8 parts of ethylenediamine;
the component B comprises the following components in parts by weight: 5-15 parts of 4,4' -dicyclohexylmethane diisocyanate, 8-15 parts of sulfonated polyether polyol, 5-15 parts of 1, 6-hexanediol adipate and 4-8 parts of trehalose.
Further, the adhesive comprises a component A and a component B:
the component A comprises the following components in parts by weight: 20-25 parts of isophorone-diisocyanate, 5-8 parts of polycaprolactone diol, 0.5-2 parts of dibutyltin dilaurate, 1-3 parts of dimethylolbutyric acid, 4-6 parts of acetone, 4-2 parts of water-based anionic polyurethane dispersion U540.5, 2-4 parts of triethylamine and 4-6 parts of ethylenediamine;
the component B comprises the following components in parts by weight: 5-10 parts of 4,4' -dicyclohexylmethane diisocyanate, 8-12 parts of sulfonated polyether polyol, 10-15 parts of 1, 6-hexanediol adipate and 4-6 parts of trehalose.
Further, the equivalent ratio of hydroxyl groups contained in the A component to isocyanate groups contained in the B component of the two-component polyurethane adhesive is 1: 0.2 to 1: 5.
On the other hand, the preparation method of the high-performance bi-component polyurethane adhesive comprises the following steps:
(1) weighing isophorone-diisocyanate into a reaction bottle, dehydrating, adding catalysts of dibutyltin dilaurate and polycaprolactone diol, reacting at a constant temperature of 60-70 ℃ for 1-2 h, adding acetone to reduce viscosity, adding dimethylolbutyric acid, reacting at a constant temperature for 1-2 h, cooling, adding triethylamine to neutralize, adding premixed aqueous anionic polyurethane dispersion U54 and deionized water under high-speed stirring, emulsifying for 10-20 min, adding ethylenediamine to extend chain for 50-70 min, and finally evaporating a solvent under reduced pressure to obtain a component A;
(2) weighing 4,4' -dicyclohexylmethane diisocyanate, sulfonated polyether polyol and 1, 6-hexanediol adipate into a reaction bottle, dehydrating, adding trehalose, and reacting at a constant temperature of 70-80 ℃ for 4-6 hours to obtain a component B;
(3) and (3) mixing the component A prepared in the step (1) with the component B prepared in the step (2) to obtain the bi-component polyurethane adhesive.
Further, the stirring speed of high-speed stirring in the step (1) is 17000-18000 r/min
Further, in the preparation method, after the solvent is removed by reduced pressure distillation in the step (1), the defoaming agent and the thickening agent are added into the reaction liquid.
Further, the defoaming agent is any one of aqueous defoaming agents Afcona 2501, Afcona 2502 or Afcona 2524; the thickener is one of SHEUR and LHEUR.
The invention has the following positive effects:
1. according to the invention, the sulfonated polyether polyol and the poly adipic acid 1,6 hexanediol ester are used as main solid matter sources, and the sulfonated polyether polyol and the poly adipic acid 1,6 hexanediol ester can improve the particle size of polyurethane, so that the solid content is improved, and meanwhile, the improvement of the solid content is beneficial to the improvement of the peel strength of the bonding strength agent.
2. The invention selects the trehalose as the internal crosslinking agent, which not only can increase the particle size of the polyurethane, but also can widen the particle size distribution of the polyurethane and make the distribution uniform. The trehalose has cross-linking and chain extension effects, so that the molecular weight of the generated polyurethane is increased, molecular chains are mutually entangled, the particle size is increased, and on the other hand, the trehalose has higher rigidity, and more hydrophobic hard segment structures are formed in the polyurethane after participating in the reaction, so that the average particle size of the emulsion is increased, and the bonding strength, the water resistance and the mechanical strength of the adhesive film are greatly improved.
3. According to the invention, the sulfonic acid type chain extender dimethylolbutyric acid is selected as the hydrophilic chain extender, and the hydrophilic groups such as carboxyl and hydroxyl are contained, so that the hydration layer can be thinned, the fluidity of the emulsion is enhanced, and the viscosity of the polyurethane is reduced to a certain extent.
4. The preparation method has simple process, convenient operation and easy solvent recovery treatment, and the obtained product is applied to the shoe making industry, and has the advantages of great convenience for construction in the production process of glued shoes due to high solid content, low viscosity, high bonding strength and good water resistance, and the gluing amount of shoe materials can be reduced, thereby not only ensuring the quality, but also saving the cost.
Detailed Description
The present invention is further described in the following examples, which should not be construed as limiting the scope of the invention, but rather as providing the following examples which are set forth to illustrate and not limit the scope of the invention.
Example 1
A preparation method of a high-performance bi-component polyurethane adhesive comprises the following steps:
(1) weighing 25g of isophorone-diisocyanate into a reaction bottle, dehydrating, adding 1g of dibutyltin dilaurate serving as a catalyst and 6g of polycaprolactone diol, and reacting at the constant temperature of 65 ℃ for 1.5 h; adding 5g of acetone to reduce viscosity, adding 2g of dimethylolbutyric acid to perform constant temperature reaction for 1.5h, cooling, adding 4g of triethylamine to neutralize, transferring to a stirrer, stirring at a high speed at a rotating speed of 17000r/min, adding 1g of premixed aqueous anionic polyurethane dispersion U54 and 8g of deionized water, emulsifying for 15min, adding 5g of ethylenediamine to extend chain for 60min, and finally performing reduced pressure evaporation to remove the solvent to obtain a component A;
(2) weighing 8g of 4,4' -dicyclohexylmethane diisocyanate, 10g of sulfonated polyether polyol and 12g of 1, 6-hexanediol adipate into a reaction bottle, adding 5g of trehalose serving as a crosslinking agent, and reacting at the constant temperature of 75 ℃ for 5 hours to obtain a component B. And then, determining and analyzing the content of isocyanate groups in the synthesized curing agent by adopting an acetone-di-n-butylamine titration method.
(3) And (2) mixing the component A prepared in the step (1) and the component B prepared in the step (2) in an amount that the equivalent ratio of hydroxyl contained in the component A to isocyanate contained in the component B of the two-component polyurethane adhesive is 1: 2.
Example 2
A preparation method of a high-performance bi-component polyurethane adhesive comprises the following steps:
(1) weighing 15g of isophorone-diisocyanate into a reaction bottle, dehydrating, adding 0.5g of catalyst dibutyltin dilaurate and 10g of polycaprolactone diol, and reacting at a constant temperature of 60 ℃ for 1 h; adding 4g of acetone to reduce viscosity, adding 1g of dimethylolbutyric acid to perform constant temperature reaction for 1h, cooling, adding 4g of triethylamine to neutralize, transferring to a stirrer, stirring at a high speed at a rotating speed of 17000r/min, adding 1g of premixed aqueous anionic polyurethane dispersion U54 and 8g of deionized water, emulsifying for 15min, adding 5g of ethylenediamine to extend chain for 60min, and finally performing reduced pressure evaporation to remove the solvent to obtain a component A;
(2) weighing 5g of 4,4' -dicyclohexylmethane diisocyanate, 10g of sulfonated polyether polyol and 8g of 1, 6-hexanediol adipate into a reaction bottle, adding 4g of trehalose serving as a crosslinking agent, and reacting at the constant temperature of 75 ℃ for 5 hours to obtain a component B. And then, determining and analyzing the content of isocyanate groups in the synthesized curing agent by adopting an acetone-di-n-butylamine titration method.
(3) And (2) mixing the component A prepared in the step (1) and the component B prepared in the step (2) in an amount such that the equivalent ratio of hydroxyl contained in the component A to isocyanate contained in the component B of the two-component polyurethane adhesive is 1: 0.2.
Example 3
A preparation method of a high-performance bi-component polyurethane adhesive comprises the following steps:
(3) weighing 30g of isophorone-diisocyanate into a reaction bottle, dehydrating, adding 3g of dibutyltin dilaurate serving as a catalyst and 10g of polycaprolactone diol, and reacting at the constant temperature of 70 ℃ for 2 hours; adding 8g of acetone to reduce viscosity, adding 3g of dimethylolbutyric acid to perform constant temperature reaction for 2 hours, cooling, adding 6g of triethylamine to neutralize, transferring to a stirrer, adding 1g of premixed aqueous anionic polyurethane dispersoid U54 and 10g of deionized water at the rotating speed of 17000r/min, emulsifying for 15min, adding 8g of ethylenediamine to extend chain for 60min, and finally performing reduced pressure evaporation to remove the solvent to obtain a component A;
(4) weighing 15g of 4,4' -dicyclohexylmethane diisocyanate, 15g of sulfonated polyether polyol and 15g of 1, 6-hexanediol adipate into a reaction bottle, adding 8g of trehalose serving as a crosslinking agent, and reacting at the constant temperature of 80 ℃ for 5 hours to obtain a component B. And then, determining and analyzing the content of isocyanate groups in the synthesized curing agent by adopting an acetone-di-n-butylamine titration method.
(3) And (2) mixing the component A prepared in the step (1) and the component B prepared in the step (2) in an amount that the equivalent ratio of hydroxyl contained in the component A to isocyanate contained in the component B of the two-component polyurethane adhesive is 1: 1.
Example 4
A preparation method of a high-performance bi-component polyurethane adhesive comprises the following steps:
(1) weighing 25g of isophorone-diisocyanate into a reaction bottle, dehydrating, adding 1g of dibutyltin dilaurate serving as a catalyst and 10g of polycaprolactone diol, and reacting at the constant temperature of 65 ℃ for 1.5 h; adding 5g of acetone to reduce viscosity, adding 2g of dimethylolbutyric acid to perform constant temperature reaction for 1.5h, cooling, adding 4g of triethylamine to neutralize, transferring to a stirrer, adding 1g of premixed aqueous anionic polyurethane dispersion U54 and 10g of deionized water at the rotating speed of 17000r/min, emulsifying for 15min, adding 5g of ethylenediamine to extend chain for 60min, and finally performing reduced pressure evaporation to remove the solvent to obtain a component A;
(2) weighing 5g of 4,4' -dicyclohexylmethane diisocyanate, 10g of sulfonated polyether polyol and 12g of 1, 6-hexanediol adipate into a reaction bottle, adding 5g of trehalose serving as a crosslinking agent, and reacting at the constant temperature of 75 ℃ for 5 hours to obtain a component B. And then, determining and analyzing the content of isocyanate groups in the synthesized curing agent by adopting an acetone-di-n-butylamine titration method.
(3) And (2) mixing the component A prepared in the step (1) and the component B prepared in the step (2) in an amount that the equivalent ratio of hydroxyl contained in the component A to isocyanate contained in the component B of the two-component polyurethane adhesive is 1: 4.
Example 5
A preparation method of a high-performance bi-component polyurethane adhesive comprises the following steps:
(1) weighing 25g of isophorone-diisocyanate into a reaction bottle, dehydrating, adding 1g of dibutyltin dilaurate serving as a catalyst and 6g of polycaprolactone diol, and reacting at the constant temperature of 65 ℃ for 1.5 h; adding 5g of acetone to reduce viscosity, adding 2g of dimethylolbutyric acid to perform constant temperature reaction for 1.5h, cooling, adding 4g of triethylamine to neutralize, transferring to a stirrer, adding 1g of premixed aqueous anionic polyurethane dispersion U54 and 10g of deionized water at the rotating speed of 17000r/min, emulsifying for 15min, adding 5g of ethylenediamine to extend chain for 60min, and finally performing reduced pressure evaporation to remove the solvent to obtain a component A;
(2) weighing 12g of 4,4' -dicyclohexylmethane diisocyanate, 10g of sulfonated polyether polyol and 6g of 1, 6-hexanediol adipate into a reaction bottle, adding 5g of trehalose serving as a crosslinking agent, and reacting at the constant temperature of 75 ℃ for 5 hours to obtain a component B. And then, determining and analyzing the content of isocyanate groups in the synthesized curing agent by adopting an acetone-di-n-butylamine titration method.
(3) And (2) mixing the component A prepared in the step (1) and the component B prepared in the step (2) in an amount that the equivalent ratio of hydroxyl contained in the component A to isocyanate contained in the component B of the two-component polyurethane adhesive is 1: 5.
Comparative example 1
Compared with the example 1, the component A does not contain dimethylolbutyric acid, and the rest is the same;
comparative example 2
Compared with the example 1, the trimethylolpropane in the component B replaces the trehalose, and the rest is the same;
comparative example 3
Compared with the example 1, the component B does not contain trehalose, and the rest is the same;
and (3) performance testing:
the samples of examples 1 to 5 and comparative examples 1 to 3 were subjected to the following tests of the index, and the results are shown in Table 1 below.
(1) Solid content: weighing 1.0-1.5g of the sample in a weighed weighing bottle, drying to constant weight, and calculating the solid content;
(2) viscosity: measured according to GB/T4851-84;
(3) initial adhesion: as determined in GB/T2791-1995; coating the emulsion between PVC/PVC film composite films, drying, and testing the T-peel strength;
(4) water resistance: observing after putting into water with the temperature of 50 ℃ for 24 hours;
(5) heat resistance: cleavage was observed at a temperature of 80 ℃.
Table 1 results of performance testing
From the results in table 1, the two-component polyurethane adhesive prepared in the embodiments 1 to 5 of the present invention has a solid content of 60% to 63%, a viscosity of 210mpa.s to 310mpa.s, a peel strength of 9.1N to 10.3N, water resistance, no blushing and falling, heat resistance, no cracking after 54 to 73min, and good performance results. And from the results of examples 1-5, it can be seen that the two-component polyurethane adhesive prepared in example 1 has the best performance.
Comparative example 1 the effect of dimethylolbutanoic acid was examined. The viscosity of the two-component polyurethane adhesive prepared in comparative example 1 increased to 710mpa.s, which was abruptly increased as compared to example 1, and the solid content and heat resistance were decreased.
Comparative examples 2-3 examine the effect on viscosity when trehalose was used as an internal crosslinking agent. Comparative example 2 when trimethylolpropane is used instead of trehalose, the solid content of the prepared two-component polyurethane adhesive is reduced to 51%, and the viscosity and heat resistance are also deteriorated; when the component B does not contain the trehalose internal crosslinking agent, the solid content of the two-component polyurethane adhesive prepared in the comparative example 3 is reduced to 43 percent, and the water resistance and the heat resistance are the worst.
Therefore, the results show that the two-component polyurethane adhesive prepared by the invention has excellent performance, high solid content, low viscosity, strong bonding force, good water resistance and heat resistance.
Claims (5)
1. The high-performance bi-component polyurethane adhesive is characterized by comprising a component A and a component B:
the component A comprises the following components in parts by weight: 15-30 parts of isophorone-diisocyanate, 5-10 parts of polycaprolactone diol, 0.5-3 parts of dibutyltin dilaurate, 1-3 parts of dimethylolbutyric acid, 4-8 parts of acetone, 4-2 parts of water-based anionic polyurethane dispersion U540.5, 1-6 parts of triethylamine and 4-8 parts of ethylenediamine;
the component B comprises the following components in parts by weight: 5-15 parts of 4,4' -dicyclohexylmethane diisocyanate, 8-15 parts of sulfonated polyether polyol, 5-15 parts of 1, 6-hexanediol adipate and 4-8 parts of trehalose;
the equivalent ratio of hydroxyl contained in the component A to isocyanate group contained in the component B of the bi-component polyurethane adhesive is 1: 0.2 to 1: 5;
the preparation method of the bi-component polyurethane adhesive comprises the following steps:
(1) weighing isophorone-diisocyanate into a reaction bottle, dehydrating, adding catalysts of dibutyltin dilaurate and polycaprolactone diol, reacting at a constant temperature of 60-70 ℃ for 1-2 h, adding acetone to reduce viscosity, adding dimethylolbutyric acid, reacting at a constant temperature for 1-2 h, cooling, adding triethylamine to neutralize, adding premixed aqueous anionic polyurethane dispersion U54 and deionized water under high-speed stirring, emulsifying for 10-20 min, adding ethylenediamine to extend chain for 50-70 min, and finally evaporating a solvent under reduced pressure to obtain a component A;
(2) weighing 4,4' -dicyclohexylmethane diisocyanate, sulfonated polyether polyol and 1, 6-hexanediol adipate into a reaction bottle, dehydrating, adding trehalose, and reacting at a constant temperature of 70-80 ℃ for 4-6 hours to obtain a component B;
(3) and (3) mixing the component A prepared in the step (1) with the component B prepared in the step (2) to obtain the bi-component polyurethane adhesive.
2. The two-component polyurethane adhesive of claim 1, comprising component a and component B:
the component A comprises the following components in parts by weight: 20-25 parts of isophorone-diisocyanate, 5-8 parts of polycaprolactone diol, 0.5-2 parts of dibutyltin dilaurate, 1-3 parts of dimethylolbutyric acid, 4-6 parts of acetone, 4-2 parts of water-based anionic polyurethane dispersion U540.5, 2-4 parts of triethylamine and 4-6 parts of ethylenediamine;
the component B comprises the following components in parts by weight: 5-10 parts of 4,4' -dicyclohexylmethane diisocyanate, 8-12 parts of sulfonated polyether polyol, 10-15 parts of 1, 6-hexanediol adipate and 4-6 parts of trehalose.
3. The two-component polyurethane adhesive with high performance as claimed in claim 1, wherein the stirring speed of the high-speed stirring in step (1) is 17000-18000 r/min.
4. The two-component polyurethane adhesive according to claim 1, wherein the step (1) further comprises adding an antifoaming agent and a thickening agent to the reaction solution after removing the solvent by distillation under reduced pressure.
5. The two-component polyurethane adhesive of claim 4, wherein the defoaming agent is one of aqueous defoaming agent Afcona 2501, Afcona 2502 or Afcona 2524; the thickener is any one of SHEUR or LHEUR.
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| JPH0881671A (en) * | 1994-09-14 | 1996-03-26 | Sunstar Eng Inc | Two pack type aqueous adhesive |
| US6797764B2 (en) * | 2000-02-03 | 2004-09-28 | Olin Corporation | Water-based adhesive |
| CN100383178C (en) * | 2005-11-15 | 2008-04-23 | 华南理工大学 | Bicompenent high solid content aqueous polyurethane, its preparation method and application |
| CN101649036B (en) * | 2009-08-20 | 2011-12-28 | 广州市合工大实力新材料研究院有限公司 | polyisocyanate curing agent and preparation method thereof |
| CN102863938B (en) * | 2012-09-05 | 2013-11-13 | 上海九元石油化工有限公司 | Preparation method of adhesive for automotive trim |
| CN104829809A (en) * | 2014-02-11 | 2015-08-12 | 王祖文 | High-molecular foam material |
| CN104194706A (en) * | 2014-08-25 | 2014-12-10 | 烟台联成高分子材料有限公司 | Double-component water-based polyurethane adhesive and preparation method thereof |
| CN104231209B (en) * | 2014-09-26 | 2017-04-12 | 江苏日出化工有限公司 | Preparation method for high-hardness waterborne polyurethane dispersion |
| DE102016122620B4 (en) * | 2016-11-23 | 2019-08-14 | Lisa Dräxlmaier GmbH | Use of an aqueous solution for accelerating the curing of polyurethane resin compositions, and methods for accelerated curing of polyurethane resin compositions |
| CN106675492A (en) * | 2017-01-06 | 2017-05-17 | 上海汉司实业有限公司 | Single-component waterborne polyurethane automotive trim adhesive and preparation method thereof |
| CN107022297B (en) * | 2017-04-15 | 2019-08-02 | 湖北铁神新材料有限公司 | A kind of water-fast aqueous polyurethane coating with bi component and preparation method thereof |
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Application publication date: 20200710 Assignee: Foshan Junneng Huanxin Technology Co.,Ltd. Assignor: JUNNENG CHEMICAL (LONGNAN) CO.,LTD. Contract record no.: X2023980042856 Denomination of invention: A high-performance two component polyurethane adhesive and its preparation method Granted publication date: 20220318 License type: Common License Record date: 20230928 |